Chapter 1

Introduction

1.1 Introduction
Energy is an essential input for industrialization, social development, economic growth and human
welfare for improving the quality of life. In the current scenario, the major energy demands
fulfilled by coal, natural gas and petroleum products. Among all the energy sources, the petroleum
products play a vital role in industries, agriculture and transportation sector. With the increasing
trend of modernization and technological development, the world energy demand is growing at a
faster rate. As a consequence, depletion of energy resources, rise of energy demand and escalating
prices of crude oil are making conditions worse. Thus, it is clear that the traditional ways of energy
sources, are no longer sustainable.

Besides this, India being a developing country requires much higher level of energy to sustain its
rate of progress. There is a limited quantum of petroleum-based mineral oil available at present.
Even with the recent discoveries and increased extraction, India imported more than 189 million
tons of crude oil in the year 2016-2017. Thus, vast dependency upon other countries for fulfilling
the petroleum product needs. The country is thus facing a dilemma because it cannot afford to
import more petroleum oil to maintain development, nor discard the petroleum-fueled prime
movers. This valuable foreign exchange could otherwise be utilized in some other development
work.

Lastly, environmental pollution has become a serious issue all around the world. This is mainly
caused by the use of the fossil fuels. Pollutants from IC engines include carbon monoxide, carbon
dioxide, sulfur dioxide, nitrogen oxides, and particulate matter. The NOX and PM are the two
primary pollutants of diesel engines. These emissions are resulting in global climate change and
responsible for local air pollution. The world is presently confronted with the twin crisis of fossil
fuels depletion and environmental degradation. Moreover, indiscriminate and lavish consumption
of fossil fuels has led to reduction in underground carbon-based resources. The large scale
utilization of fossil fuels is also putting significant stress on the environment. The effects of
combustion products on air quality and the climate are both local and global in nature. The local
effects primarily are the form of air pollution and smog formation in urban areas. On a global scale,
1
there is increasing evidence, and concern about the role of carbon dioxide (greenhouse gases) on
global climate change. Thus, the government has made strong emission protocol and standards for
vehicles as well as emission regulations for the big industries.

All the above listed concerns are the driving force to develop non-petroleum, renewable,
biodegradable, non-toxic and non-polluting alternative fuels. It has become mandatory to discover
fuels in support to conventional diesel fuels for protecting the global environment and concern for
long term supplies of conventional diesel fuels. The need for diversifying towards alternative
energy choices is increasingly being recognized as inevitable, particularly to enhance energy
security, given the uncertainties and constraints associated with conventional fuels and
technologies. Rapid deployment of renewables together with improvements in energy efficiency
can contribute to much higher levels of energy security while generating significant employment
opportunities and simultaneously ensuring lower levels of air pollution with associated health
benefits.

This dissertation is aimed to seek the possibility of development of the three different biofuel
(biodiesel, hydro processed fuel & hybrid fuel) from waste cooking oil which can be further used
as substitute either partially or fully to that of diesel. This investigation deals with: parametric
optimization of the biofuel; comparative analysis of physio-chemical characteristics of the biofuels
with that of diesel and each other; a detailed experimental analysis of combustion, performance
and emissions of the produced biofuels in a CI engine without or with modification in the injection
pressure and injection timings.

1.2 Global energy scenario

Figure 1.1 shows the world energy consumption from year 1992 to 2017. This figure illustrates
all type of energy resources viz. coal, renewable energy source, hydroelectricity, nuclear energy,
natural gas & oil. The primary energy consumption increased intensely in 2017, which is led by
natural gas and renewables with coal’s share of the energy mix continuing to decline. In 2017, the
primary energy consumption growth averaged increased by 1.2% from previous year and the
fastest since 2013. The average cost of oil was $54.19 per barrel in 2017 which is increased from
$43.73/barrel in 2016. This was the highest increase in oil price/barrel since 2012. The global oil
consumption growth extended to 1.7 million barrel per day i.e. average increase by 1.8% from the
2
average of last 10 years. China (500,000 b/d) and the US (190,000 b/d) were the single largest
consumer of oil, followed by India and Japan.

Source: BP statistical review of world energy 2018

Figure 1. 1 World energy consumption

The natural gas consumption extended to 96 billion cubic meters (bcm) i.e. increased by 3%, fastest
since 2010. The natural gas consumption growth was driven by China (31 bcm), the Middle East
(28 bcm) and Europe (26 bcm). Moreover, the natural gas consumption is reduced in the US by 11
billion cubic meter (1.2%) from the previous year (2016). The coal consumption increased by 25

3
million tonnes of oil equivalent (mtoe), or 1%, the first growth since 2013. The consumption
growth was driven largely by India (18 mtoe), whereas coal consumption of China is also slightly
increased by 4 Mtoe after following three successive annual declines during 2014-2016. The
renewable power (includes solar, wind and bio-mass) grew by 17%, higher than the 10-year
average and the largest increment on record (69 mtoe)(British Petroleum, 2018).

1.3 Indian energy scenario

1.3.1 Availability of energy reservoir at India
India is the third largest energy consumer in the world and the country’s energy consumption is likely
to be increase in the future. As per Indian statistical energy report 2018, the estimated reserves of coal
were 315.14 billion tonnes as calculated on 31.03.2017, there is an increase of 6.34 billion tonnes (2.05
%) of coal reservoirs during the year 2016-2017.

Table 1. 1: Net import and export of Coal, crude oil and petroleum products in India

Millions of tones

Year Coal Crude oil Petroleum Products

Gross Exports Net Gross Exports Net Gross Exports Net

import Imports imports Imports imports Imports
s
2007-08 49.79 1.63 48.17 121.67 0.00 121.67 22.46 40.75 -18.29
2008-09 59.00 1.66 57.35 132.78 0.00 132.78 18.59 38.94 -20.36
2009-10 73.26 2.45 70.81 159.26 0.00 159.26 14.67 51.16 -36.49
2010-11 68.92 1.88 67.04 163.60 0.00 163.60 17.38 59.08 -41.70
2011-12 102.85 2.02 100.84 171.73 0.00 171.73 15.85 60.84 -44.99
2012-13 145.79 2.44 143.34 184.80 0.00 184.80 16.35 63.41 -47.05
2013-14 166.86 2.19 164.67 189.24 0.00 189.24 16.70 67.86 -51.17
2014-15 212.10 1.24 210.87 189.43 0.00 189.43 21.30 63.93 -42.63

2015-16 203.95 1.58 202.37 202.85 0.00 202.85 29.46 60.54 -31.08
2016-17 190.95 1.77 189.18 213.93 0.00 213.93 36.29 65.51 -29.23
Growth Rate of - 27.22 -4.03 5.46 - 5.46 12.57 8.22 -5.97
2016-2017 over 3.84
2015-2016 (%)
Source: Indian statistical energy report 2018

4
Beside this, the estimated reserves of crude oil in India was 604.10 million tonnes (MT) as calculated
on 31.03.2017, which is reduced by 17.18 million tonnes (2.76 %) from the previous year (621.28
million tonnes). The net import and export of coal, crude oil, and petroleum products in the last 10
years are presented in the Table 1.1. In the past, India derived most of its energy from coal, but
presently the country has been exploring different energy resources to fulfill the energy demand.
However, fossil fuels are still the largest and viable energy source (Energy statatics of India et al.,
2018).

1.3.2 Refineries in India

India is highly dependent on import of crude oil as shown in the Table 1.1. The net imports of
crude oil have increased from 121.67 MTs during 2007-08 to 213.93 MTs during 2016-17. There
has been an increase of 5.46% in the net imports of crude oil during 2016-17 over 2015-16, as the
net import increased from 202.85 MTs to 213.93 MTs. The export of petroleum products has
increased from 40.75 MT during 2007-08 to 65.51 MTs during 2016-17. During 2016-17, exports
recorded an increase of 8.22% from previous year. The import of petroleum products has increased
to 36. 29 MT from 22.46 MT in 2016-17 over the year 2006-2007. Although there are some
variations in the trend, there growth rate is increased by 12.57% in import of petroleum products
over the previous year (2015-16). In India, 23 refineries have been established over a period of
time, out of which, 18 are in the Public Sector, 3 in the Private sector and 2 in Joint Venture. These
refineries are gearing up for better fuel quality to meet Euro or ASTM standards. The refining
capacity of these refineries were 234 MMT on 31.03.2017, which is approximate 4 MMT higher
than the country’s refining capacity (230 MMT) on 31.03.2016. The Refinery production (crude
throughput) quantity was 245.362 MMT during 2016-17 which indicates net increase of 5.4% over
2015-16 (232.865 MMT). The capacity utilization of the refineries reduced from 108.3% to 106.6
% during 2016-17 over the previous year 2015-16.
The production of Petroleum Products in the country was increased to 243.55 MTs during 2016-
17 from 231.92 MTs during 2015-16, which is increased by 5.02%. In India, high speed diesel oil
(maximum share – 42.08%), followed by Motor Gasoline (15.02%) are the major petroleum
products consumed during 2016-17. The net production of Natural Gas decreased from 31.24
billion cubic meters (BCM) during 2015-16 to 30.92 BCM during 2016-17, which is decreased by
1.03% (Energy statatics of India et al., 2018).
5
1.4 Air Quality index
Air pollution is identified as a global risk factor for disease. In the last few decades, the research
conducted in numerous cities throughout the world shows that more number of people either dying
or suffer from serious diseases, when air pollution levels increases. Moreover, studies reported that
long-term exposure to air pollution prove that people living in more polluted areas die prematurely,
compared with those living in areas with lower levels of pollution. Research also provides details
on how air pollution affects human health, with evidence clearly showing impacts on the rates of
cardiovascular disease, stroke, asthma, effecting eyes and more difficult to breathe that leads to
disease of respiratory system. Exposure to PM2.5, become the environmental risk factor for death.
About 4.2 million deaths are reported from inhalation of PM2.5, which ranks 5th worldwide among
all risks, including high blood pressure, smoking, high glucose, and cholesterol level as shown in
the Fig. 1.2.

6
 Source: state of global air/2017
Figure 1. 2 Global ranking of risk factors for total deaths from more frequent causes

In 2015, highest concentrations of PM2.5 were observed in North Africa and the Middle East, which
are mainly due to high levels of windblown mineral dust. At the country level, estimates of PM2.5
concentrations in 2015 were highest in Qatar (107 μg/m3), Saudi Arabia (106 μg/m3), and Egypt
(105 μg/m3). The next highest concentrations appear in South Asia (especially northern India and
Bangladesh) and Southeast Asia, eastern China, and Central and Western sub-Saharan Africa, this
is mainly due to combustion emissions from multiple sources, including household solid fuel use,
coal, thermal power plant, agricultural, manufacturing industries, and transportation-vehicles. The
population-weighted annual average concentrations were 89 μg/m3 in Bangladesh, 75 μg/m3 in
Nepal, and 74 μg/m3 in India. The population-weighted average PM2.5 concentrations in China was

7
58 μg/m3, with substantial variation in concentrations among provinces (19–79 μg/m3) (State of
Global Air 2017).

1.5 Global warming

Scientists came to know that there are certain gases which trap heat and act like a blanket to warm
the earth surface temperature. Carbon dioxide (CO2) is the most heat trapping gas, which is
released into the atmosphere due to burning of fossil fuels such as oil, coal, and thermal power
plant, natural gas, vehicles etc. The CO2 also absorbs heat which is reflected from the Earth’s
surface that would otherwise pass freely into space. As the atmosphere is overloaded with carbon
dioxide, more amount of heat is trapped and Earth surface temperature starts to rise. Satellite
measurements confirm that less heat is escaping from the atmosphere to space as compared to 40
years ago. Although other heat-trapping gases also play a role, CO2 is the main contributor to
global warming. It has been analyzed from statistical data that every one of the past 40 years has
been warmer than the 20th century average (International Energy Agency report 2018). Moreover,
12 warmest years were recorded since 1998. The year 2016 was the hottest year on record. Over
the past 130 years, the earth surface average temperature has increased by 1.5 degrees Fahrenheit,
with more than half of that increase occurring over only the past 35 years. The detailed
measurements of atmospheric carbon dioxide (CO2) levels have been taken regularly since the late
1950s. In 2017, there is 28 % increase in CO2 as compared to 1959. In the past, there were number
of activities has been taken due to natural causes such as volcanic activity, changes in the sun’s
intensity, fluctuations in Earth's orbit, and other natural disasters, but none of the activity account
for the current rise in earth surface temperature. Now, scientists can conclusively identify that
human activity is responsible for the increase in CO2 level in the atmosphere. The carbon dioxide
emitted by various source such as: burning coal, natural gas, and oil has a unique chemical
“fingerprint" — and the additional CO2 in the atmosphere bears that signature.

The Intergovernmental Panel on Climate Change (IPCC) was established in 1988 by the World
Meteorological Organization (WMO) and the United Nations Environment Programme (UNEP)
to assess climate change based on the latest science and technology. In IPCC, thousands of experts
around the world synthesize the most recent developments in climate science, adaptation,
susceptibility, and moderation every five to seven years. The IPCC has issued comprehensive
8
assessments in 1990, 1996, 2001, 2007 and 2013, plus methodology reports, technical papers, and
periodic special reports assessing specific impacts of climate change.

1.6 Need for alternative resource of energy

In 1973 OPEC (organization of petroleum exporting countries, founded in 1960) put an embargo
on oil production and started an oil pricing control strategy. The oil prices increased four times
causing severe energy crisis around the world. This resulted in spiraling price rise of various
commercial energy sources leading to global inflation. The world paid attention to this energy
crisis very seriously and for the first time a need for developing alternative sources of energy was
felt. All the other alternate energy sources were getting considerations and huge amount of funds
were allocated for exploring and development of these resources. Thus, 1973 is considered as the
year of the first “oil shock”. Two more “oil shocks” jolted the world in 1979 and 1990, which
further focused the attention on alternate energy sources.
The limited reserves of fossils fuel have been the matter of global concern as these are under threat
of extinction due to over exploitation. Beside this, deteriorating environmental conditions have
become an issue of ever increasing worldwide public sources of CO2 emission. The continuous
efforts are taken around the globe to protect the environment from further deterioration. These
factors have led to an innovative global search for renewable sources of energy. Consequently,
some alternatives, particularly renewable energy options, have been explored and discovered. In
India, there is high potential for generation of renewable energy from various sources such as:
wind, solar, biomass, small hydro and cogeneration bagasse. In India, the total potential for
renewable power generation was 1001.14 GW as calculated on 31.03.17. This includes potential
of solar power – 649.34 GW (64.86%), Wind power – 302.25 GW (30.19%) at 100 m hub height,
SHP (small-hydro power) – 21.134 GW (2%), Biomass power – 18.601 GW (1.86%), Bagasse-
based cogeneration in sugar mills – 7.260 GW (0.73%), and from waste to energy - 2.554 GW
(0.26%) (Energy statatics of India et al., 2018).

1.7 Global biofuel trends & polices

The biofuel has been accepted worldwide mainly due to its remarkable advantages. The Table 1.2
represents the consumption of biofuels at world levels. The United states, Brazil and Europe are
the main nations which accelerates the biofuel consumption intensively at higher rate as compared
9
 to the others. Moreover, the strong biofuel polices have been made by most of the counties to
replace the fossil fuels with renewable biofuels. The United States began polices in regard
to biofuels, such as ethanol fuel and biodiesel in the early 1990s. The government began looking
more intensely at biofuels to reduce dependence on foreign oil and increase the nation's
overall sustainability. In the United States, the biofuel usage quantity is decided by Renewable
Fuel Standard (RFS), whereby a minimum volume of biofuels is to be used in the national
transportation fuel supply each year. Congress established the RFS in Title XV, Subtitle A, Section
1501 of the Energy Policy Act of 2005 (Pub.L. 109–58). This initial RFS (referred to as RFS1)
mandated that a minimum of 4 billion US gallons (15,000,000 m3) be used in 2006, and that this
minimum usage volume increase to 7.5 billion US gallons (28,000,000 m3) by 2012. Two years
later, Congress passed the Energy Independence and Security Act of 2007 (Pub.L. 110–140). The
provisions in the act amended the provisions in EP Act 2005 and expanded the biofuels blending
mandate. The expanded RFS (referred to as RFS2) required the annual use of 9 billion US gallons
(34,000,000 m3) of biofuels in 2008 and expanded the mandate to 36 billion gallons annually in
2022.

In Brazil, The National Alcohol Program (PROÀLCOOL) was started by a Presidential Decree in
1975 in response to continue hike in oil prices. The percentage of ethanol blended in gasoline could
vary from 18 to 25 percent according to the Provisional Measure #532 of April 2011. In 2011, the
ethanol blend percentage was reduced from E25 to E20 due to lower availability. Again, in June
2012, E25 was reinstated and in 2015 Brazil implemented a resolution for the blend of ethanol in
gasoline to be 27%. The National Council of Energy Policy (Conselho Nacional de Politica
Energética, CNPE) consequently introduced a number of resolutions to realize the requirements
of Law 11.097. Resolution #2 of March, 2008 set a 3% requirement as of July 2008; Resolution
#2 of April, 2009 set a 4%

Table 1. 2: Globally consumption of biofuels

Thousand tonnes oil equivalent
2010 2011 2012 2013 2014 2015 2016 2017 Growth Rate
2016-2017
(%)
US 28044 31184 29808 31057 32890 33849 35986 32936 2.9

10
Canada 787 899 1004 1059 1188 1142 1197 1239 3.8
Mexico 10 13 9 7 7 5 14 14 -
Total North 28841 32095 30821 32124 34086 34996 37197 38190 3.0
America
Argentina 1670 2234 2295 2014 2644 2038 2828 3131 11.0
Brazil 16866 14403 14739 17114 18008 19332 18168 18465 1.9
Colombia 455 572 627 650 676 693 626 617 -1.1
Other S. & 232 313 304 359 382 385 409 456 11.8
Cent America
Total S. & 19223 17522 17965 20136 21707 2248 22030 22669 3.2
Cent. America
Austria 391 390 390 374 329 381 419 391 -6.5
Belgium 523 525 536 526 666 482 477 471 -1.0
Finland 301 208 263 330 367 432 109 219 101.9
France 2353 1935 2145 2306 2573 2559 2405 2224 -7.3
Germany 3022 2967 3031 2770 3460 3191 3228 3293 2.3
Italy 678 486 298 454 575 572 600 595 -0.5
Netherlands 391 674 1276 1495 1980 1816 1477 1658 12.6
Poland 439 414 652 697 750 940 928 920 -0.6
Portugal 284 330 276 274 301 321 298 315 5.9
Spain 1312 851 620 749 1030 1122 1200 1541 28.7
United 304 322 303 517 403 310 554 617 11.8
Kingdom
Other Europe 1153 1259 1413 1449 1494 1679 1745 1738 -0.1
Total Europe 11490 10761 11692 12578 14717 14028 13652 14167 4.1
Total CIS 34 28 29 23 25 19 19 19 -
Total Middle 5 5 5 5 5 5 5 5 -
East
Total Africa 8 8 23 32 40 40 40 40 -
Australia 222 223 241 210 163 162 183 144 -21.1
China 1584 1970 2103 2346 2609 2653 1811 2147 18.8
India 123 192 168 198 198 438 544 436 -19.9
Indonesia 723 1110 1397 1750 3110 1314 2238 2326 4.2
South Korea 511 309 283 321 337 385 386 406 5.3
Thailand 700 765 1054 1330 1490 1603 1610 1846 15.0
Other Asia 443 692 1067 1363 1522 1777 1767 1727 -2.0
Pacific
Total Asia 4306 5262 6313 7518 9429 8333 8540 9031 6.0
Pacific
Total World 63906 65680 66848 72415 80009 79866 81483 84121 3.5
Of which 40832 43107 42773 44936 4900 49235 51054 52552 3.2
OECD
Non-OECD 23074 22573 24074 27478 31009 30630 30429 31569 4.0
European 11387 10569 11581 1249 14638 13906 13532 14044 4.1
Union
Source: BP statistical review of world energy 2018

requirement as of July 2009 and Resolution #6 of September, 2009 set a 5% requirement as of

January 2010. In May 2014, the Minister of Mines and Energy announced that the biodiesel

11
requirement would increase to 6% on July 1, 2014 and 7% on November 1, 2014. Those
requirements have been updated to 8% in March of 2017, 9% in March of 2018, and 10% in March
of 2019, with blends of up to 15% permitted.

The European Union (EU), started implementing biofuel-related targets in 2003. The Biofuel
Directive set indicative biofuel blending targets of 2% by the end of 2005 and 5.75% by the end
of 2010. In 2009, the EU Commission passed two major directives supporting the increment of
renewable fuels extending to 2020. The Renewable Energy Directive (RED) mandates that 20%
of all energy usage in the EU, including at least 10% of all energy in road transport fuels, will be
produced from renewable sources by 2020. Alongside the RED, an amended Fuel Quality
Directive (FQD) was also passed, which will have focused on the 6% reduction of carbon than a
fossil diesel and gasoline. The both Directives are clearly targeted to reduce GHG emissions.

In India, in order to promote biofuels, a National Policy on Biofuels was made by Ministry of New
and Renewable Energy during the year 2009. Globally, biofuels are getting popularity in last few
decade and it is vital to keep up with the pace of developments in the field of biofuels. In India,
Biofuels are getting very importance as it meets well with the ongoing initiatives of the
Government such as Make in India, Swachh Bharat Abhiyan, Skill Development and offers great
opportunity to integrate with the ambitious targets of doubling of Farmers Income, Import
Reduction, Employment Generation, Waste to Wealth Creation. Biofuels programmes in India has
been largely impacted due to the sustained and quantum non-availability of domestic feedstock for
biofuel production which needs to be addressed.

In 2018, The Union Cabinet, chaired by the Prime Minister Shri Narendra Modi has approved
National Policy on Biofuels.

i. The Policy categorizes biofuels as "Basic Biofuels" viz. First Generation (1G) bioethanol
& biodiesel and "Advanced Biofuels" - Second Generation (2G) ethanol, Municipal Solid
Waste (MSW) to drop-in fuels, Third Generation (3G) biofuels, bio-CNG etc. to enable
extension of appropriate financial and fiscal incentives under each category.
ii. The Policy expands the scope of raw material for ethanol production by allowing use of
Sugarcane Juice, Sugar containing materials like Sugar Beet, Sweet Sorghum, Starch

12
 containing materials like Corn, Cassava, Damaged food grains like wheat, broken rice,
Rotten Potatoes, unfit for human consumption for ethanol production.
iii. Farmers are at a risk of not getting appropriate price for their produce during the surplus
production phase. Taking this into account, the Policy allows use of surplus food grains for
production of ethanol for blending with petrol with the approval of National Biofuel
Coordination Committee.
iv. With a thrust on Advanced Biofuels, the Policy indicates a viability gap funding scheme
for 2G ethanol Bio refineries of Rs. 5000 crores in 6 years in addition to additional tax
incentives, higher purchase price as compared to 1G biofuels.
v. The Policy encourages setting up of supply chain mechanisms for biodiesel production
from non-edible oilseeds, Used Cooking Oil, short gestation crops.
vi. Roles and responsibilities of all the concerned Ministries/Departments with respect to
biofuels has been captured in the Policy document to synergise efforts.

1.8 Alternative fuels for CI engine

In the search of the alternative fuels, biomass based resources have been derived to substitute the
petro-diesel either partially or fully. The most frequently used processes to convert the raw oil
(vegetable oil, animal fat, waste material and algae) into biofuels to make suitable for CI engine
either by chemical process or without chemical treatment are shown in the Figure 1.3

1.8.1 Straight vegetable oil

In the end of 19th century, straight vegetable oils have been used to run the CI engine. Among the
efforts involving renewable resources, the use of vegetable oil such as sunflower oil, rapeseed oil,
palm oil and sunflower are well known. Although, short term usage of vegetable oil in CI engine
showed positive results, a long term use of neat vegetable oils leads to severe engine problems due
to higher kinematic viscosity and density such as carbon deposition, oil ring sticking, incomplete
combustion and injector coking. Therefore, vegetable oils and animal fats must be subjected to
one of the following chemical treatment to reduce the viscosity and facilitate utility as liquid fuel
substitutes.

13
 Figure 1. 3 Chemical processes for the production of biofuels.

1.8.2 Direct blending

In direct blending (dilution), straight run vegetable oil is mixed with diesel in certain proportion
and fueled in the CI engine. The advantage of blending is liquid nature-portability but the
kinematic viscosity of neat vegetable oil is much higher than petro-diesel. Moreover, acid value,
FFA content, and gum formation of vegetable oil made makes it incompatible for CI engine.

1.8.3 Pyrolysis

Pyrolysis is a severe form of thermal cracking with subsequent rearrangement of fragments. It

involves heating in the absence of air with the help of appropriate catalyst. SiO2, molecular sieves,
zeolites, sodium carbonate and Al2O3 etc. are some widely used catalyst for pyrolysis. The
resulting bio-crude can be used as fuel or for the production of chemicals and other ‘‘bio-based’’
products. Though, bio-crude produced from pyrolysis is chemically similar to diesel oil but setup
required for pyrolysis is extravagant. As oxygen is removed in this process, it reduces its
environmental benefits and usually produces a fuel closer to gasoline than diesel. The product of
pyrolysis process has lesser viscosity, flash point and pour point than diesel fuel and equivalent
calorific values. However, in terms of distillate recovery the process is not very efficient (Ma and
Hanna, 1999).

14
1.8.4 Biodiesel
Biodiesel is defined as the mono-alkyl ester of fatty acids derived from vegetable oils, waste
cooking oil, micro algae, animal fats, etc. It is produced by a chemical process called
transesterification as shown in the Fig. 1.4.

Catalyst
+ 3 H3C – OH +
(Methanol))

Figure 1. 4 Transesterification Reaction

In the transesterification reaction, bio-mass based oils (vegetable oils, animal fats and recycled
restaurant greases) are chemically reacted with alcohol (usually methanol or ethanol) under the
presence of strong base alkaline catalyst (NaOH, KOH, etc.) and the final obtained product
(biodiesel) is called as methyl ester or ethyl ester of the corresponding oil used. The glycerol (also
called glycerin) is produced as a by-product. Chemically, most of the biodiesel produced consists
of alkyl esters instead of the alkanes and aromatic hydrocarbons of petroleum derived diesel.
Ideally, transesterification is primary a less expensive way of transforming the large, branched
molecular structure of the bio-oils into smaller molecules. (Rashid and Anwar 2008)(Atadashi et
al. 2012)(Jain and Sharma 2010).

1.8.5 Micro-emulsion (hybrid fuel)

Micro emulsion is defined as a colloidal equilibrium dispersion of optically isotropic fluid
microstructure with dimensions generally in 1–150 range formed spontaneously from two
normally immiscible liquids and one and more ionic or more ionic amphiphilic. In general, the
micro-emulsion process consists of introducing the chosen quantity of surfactant, co-surfactant
and water into the diesel, biodiesel or vegetable oil in appropriate proportion. It has equivalent
density, higher kinematic viscosity, and a low calorific value as compared to diesel/biodiesel. The
selection of suitable vegetable oil for micro-emulsion entirely depends upon the properties like

15
FFA, kinematic viscosity, density, and calorific value. Ethanol is though preferred over water due
to its lower density and flammability. Butanol-1 is used as surfactant due to its high calorific value
(CV), low heat of vaporization, and long term miscibility as compared with other surfactants. The
advantages of micro-emulsification approach over the chemical processes (transesterification,
pyrolysis, catalytic-cracking, etc.) include easy to handle, lower production costs, short production
time, simple and easy implementation and no by-product. In addition, due to the presence of more
oxygen content, the combustion temperature of the microemulsion fuels are much lower, which
results in a significant reduction in emissions of NOx, CO, black smoke and particulate matter
(Ileri, Atmanli, and Yilmaz 2015)(Qi et al. 2013)(Bora et al. 2015).

1.8.6 Hydroprocessed fuels

Hydrogenated fuels derived from vegetable oils or animal fats are gaining more popularity than
other biofuels mainly due to their higher calorific value, cetane index, and better storage stability.
Hydro-processing technique is being explored as an alternative approach to convert biomass
(preferably lipid) into liquid hydrocarbons (mainly C11–C18) having similar characteristics to
petroleum products. This technique requires high temperature (300–400°C) and pressure (5–120
MPa) with alkali catalysts in the presence of hydrogen atmosphere for chemical transformation of
vegetable oils into bio-crude (Popov and Kumar 2015)(Manchanda, Tyagi, and Sharma
2017)(Ogunkoya et al. 2015a). Further, the biocrude is distilled at different boiling ranges to
produce organic liquid fractions (OLFs) which mainly consisted of paraffinic hydrocarbons. These
paraffinic hydrocarbons have higher calorific value and cetane index with far better properties like
density, kinematic viscosity, flash point, etc. Besides these, as hydro-processing includes
desulfurization reactions, these fuels have very less sulfur (<5 mg/kg), nitrogen (<2 mg/kg), and
aromatic content (<1%) and low olefinic double bond-containing components (<0.2%)
(Bezergianni and Dimitriadis 2013)(Mangus, Mattson, and Depcik 2015).

16
 Figure 1. 5 Hydroprocessing reaction

Furthermore, catalyst plays an important role to enhance the rate of chemical reaction, such as
breaking down the unsaturated molecules into saturated ones, removal of heteroatom (oxygen,
sulfur, and nitrogen), acidity removal, and formation of hydrocarbons. Mainly alkali-based catalyst
such as NiMo/Al2O3, NiW/Al2O3, CaO, Na2CO3, K2CO3, alkali/alkaline earth oxide, and modified
zeolite have been used for hydro-processing (Sonthalia and Kumar 2017) (Patel and Kumar 2016)

1.9 Merits and demerits of biofuel

Since beginning of 20th century, many researchers worked on the production of different biofuels.
The following are the benefits as well as shortcoming of biofuel:

1.9.1 Advantages of Biofuels

1. Easy to Source: Biofuels are derived from easily available sources such as vegetable oil, algae,
animal fats, manure, waste from crops and plants etc.
2. Renewable in nature: Petroleum products are refined from crude oil, which is a non-renewable
resource, whereas, biofuels are derived from vegetable oil, corn, waste from crops and plants.
These all resources are renewable in nature i.e. it can be replanted again and again.
3. Reduction of Greenhouse Gases: all fossil fuels produce large amount of greenhouse gases
i.e. carbon dioxide in the atmosphere. These greenhouse gases trap sunlight and increase the
17
surface temperature of Earth. Biofuels are found to be very good option for reduction of
greenhouse gases in the atmosphere.
4. Economic Security: very few countries have the resources of crude oil in sufficient quantity.
Due to this reason, most of the countries import crude oil which puts a huge effect in the economy.
A country can reduce its dependency on crude oil by shifting towards biofuels. As a result, more
jobs will be created with a growing biofuel industry, which will keep economy more secure.
5. Cost Benefit: Biofuels almost cost the same in the market as gasoline or diesel does. Although,
the overall cost benefit of using them is much higher, biofuel are cleaner fuels, they produce fewer
emissions on burning. As demand of biofuels increase, they have a potential of becoming cheaper
in future as well.
6. Reduce dependence on foreign crude oil: The locally grown crops have potential to reduce
the nation’s dependency on fossil fuels. Moreover, as prices of crude oil is touching sky high,
biofuels are found to be a very good option to reduce dependency.
7. Lower pollution: Since biofuels can be made from renewable resources, they cause less
pollution to the atmosphere. However, that is not the only reason why the use of biofuels is being
encouraged. They release lower levels of carbon dioxide and other emissions.

1.9.2 Disadvantages of Biofuels

1. Higher production cost: Although, biofuels have ample benefits associated with surroundings,
they are still quite expensive to produce in the current market. Due to this reason, the use of
biofuels has not been very encouraging.
2. Monoculture: Monoculture refers to cultivation of same crops year after year, rather than
producing different crops through a farmer’s fields over time. This might be economically
attractive for farmers but growing same crop every year may deprive the soil of nutrients.
3. Use of Fertilizers: most of the biofuels are produced from crops and these crops need fertilizers
to grow better. The fertilizers have harmful effects on surrounding environment and may
cause water pollution.

18
4. Shortage of Food: Biofuels are extracted from plants and crops that have high levels of sugar
in them. It will take up agricultural space from other crops, which can create a number of problems.
One major worry being faced by people is that the growing crops for biofuels may result in rise in
food prices as well.
5. Industrial Pollution: The carbon footprint of biofuels is less than the traditional forms of fuel,
but production of biofuels is largely dependent on lots of water and oil. Large scale industries
meant for churning out biofuel are known to emit large amounts of emissions and cause small scale
water pollution as well.
6. Water Use: Large quantity of water is required to irrigate the biofuel crops and it may impose
strain on local and regional water resources. In order to produce corn based ethanol to meet local
demand for biofuels, large quantity of water is used that could put unsustainable pressure on local
water resources.
7. Future Rise in Price: Current technology being employed for the production of biofuels is not
efficient. Scientists are engaged in developing better and economical chemical process through
which biofuels can be produced. However, the cost of research and future installation means that
the price of biofuels will see a significant spike.

1.10 Organization of thesis

The thesis begins with an introduction giving a brief insight to the importance and urgent need of
biofuels as an alternative fuel in CI engines. Chapter 2 gives a systematic review of the available
literature on the production of biodiesel, micro-emulsion and green diesel from various feedstock’s
with their characterization and applications in the CI engine. Based upon the concluding summary
of the literature, the objective of the present study has been formulated. Chapter 3 explains the
experimental methodology for the production of biofuels, instruments for measuring the
characteristics and engine test rig for utilization of biofuels. Chapter-4 deals with results and their
analysis carried out on the production parameters for biodiesel, hybrid fuels and hydroprocessed
fuels derived from waste cooking oil, characteristics of the produced biofuels and then comparing
the behavior of engine fueled with the different biofuels with petro-diesel and each other. Chapter

19
5 presents the concluding remarks of the study which is followed by future scope of the present
work and references at the end of the chapter.

20